CN103874730B - The acrylic resin film of bend-resistance albefaction and disruptiveness excellence - Google Patents
The acrylic resin film of bend-resistance albefaction and disruptiveness excellence Download PDFInfo
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- CN103874730B CN103874730B CN201280049155.3A CN201280049155A CN103874730B CN 103874730 B CN103874730 B CN 103874730B CN 201280049155 A CN201280049155 A CN 201280049155A CN 103874730 B CN103874730 B CN 103874730B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C08J2475/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/31855—Of addition polymer from unsaturated monomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/00—Stock material or miscellaneous articles
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Abstract
The object of the invention is to, provide a kind of film being applicable to decorated molded purposes, when its molding at plastics etc. carrying out lamination, bending albefaction is few, surface hardness is high, the transparency is excellent and the physical property of fracture-resistant excellence balances.Wherein, methacrylic resin composition (D) is carried out membranization and form acrylic resin film, described methacrylic resin composition (D) is containing specific methacrylate-based resin (A), graft inter polymer (B) containing rubber and the graft copolymer (C) containing rubber, the described graft inter polymer (B) containing rubber is 4 segment structure polymkeric substance and the averaged particles footpath of rubber particles is 0.2 ~ 0.4 μm, the described graft copolymer (C) containing rubber is 2 Rotating fields polymkeric substance and the averaged particles footpath of rubber particles is 0.02 ~ 0.15 μm.
Description
Technical field
The present invention relates to the acrylic resin film of balancing good of fracture-resistant, surface hardness and bend-resistance albefaction.
Technical background
The acrylic resin film that acrylic resin composition machine-shaping containing cross-linked elastomer is formed, be widely used in using its transparency and hardness as in the various purposes of feature.Include, for example, the purposes substituted as application and being pressed on by rete automobile interior exterior decorative element uses or as carrying and the external decoration of family's electrical article such as laptop computer or the purposes etc. of building plane materiel.As the method for decorating the surface of plastics, there is the mould inner membrance method of forming, namely on the films such as acrylic resin, give shape in advance by vacuum forming etc., or with the state of not giving, to embed in injection moulding metal die and substrate resin is carried out injection moulding.About the acrylic resin film being applicable to such use has various motion.Such as, there are known, the method (patent documentation 1) of the particle diameter, rubber content etc. of the regulation reduced viscosity of moldable polymer, the polymkeric substance containing rubber, the method (patent documentation 2 and 3) of the content of the regulation reduced viscosity of acrylic polymers, the acrylic polymers of multilayered structure.The surface hardness of these films known, the transparency and film formability are excellent.
But, about the problem of the bending albefaction of film is without any relevant record.That is, these films above-mentioned are in this purposes, film is carried out lamination by the moulded products of the shape of complexity, exist and cause the easy albefaction of film because of place's stress concentration such as turnings, thus there is the significantly reduced problem of commodity value.
As the film improved the tolerance (hereinafter referred to as bend-resistance albefaction) of bending albefaction, there will be a known the method (patent documentation 4) that the degree of crosslinking of cross-linked elastomer and the relation of particle diameter are specified.But, although bending albefaction is excellent, there is the fracture-resistant of film, the physical property balance of surface hardness do not reach the problem of optimization.In addition, the scheme proposed as the acrylic resin film with excellent solvent resistance and the transparency rubber of two types is carried out the method (patent documentation 5) admixed.But, any description is not carried out to bend-resistance albefaction, does not mention the content of any physical property about bend-resistance albefaction, fracture-resistant, surface hardness balance.In addition, even if heat as carrying out when shaping the gonorrhoea that film does not occur yet, thus maintain the acrylic resin film of apperance designability, the scheme of proposition is the method (patent documentation 6) being carried out by the rubber of two types mixing.But, in this method, not mentioning any about the content for the tolerance because bending the albefaction caused yet, so there is no the physical property balance improving resistance to bending albefaction, fracture-resistant, surface hardness.
prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 8-323934 publication
Patent documentation 2: Japanese Unexamined Patent Publication 10-279766 publication
Patent documentation 3: Japanese Unexamined Patent Publication 10-306192 publication
Patent documentation 4: Japanese Patent No. 4291994 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2002-309059 publication
Patent documentation 6: Japanese Patent No. 3835275 publication
Summary of the invention
The problem that invention will solve
To the object of the present invention is to provide when to carry out lamination on the molding etc. of plastics that bending albefaction is few, surface hardness is high, the transparency is excellent and the physical property of fracture-resistant excellence balance is good, the film that is applicable to decorated molded purposes.
The method of dealing with problems
What the present inventors inquired into repeatedly deeply found that, carries out shaping and film that is that formed, can solve the problem, thus be over into the present invention for the resin combination comprising methacrylate-based resin and the specific graft copolymer containing rubber.
Namely, the present invention is the acrylic resin film of following methacrylic resin composition (D) being carried out membranization and being formed, described methacrylic resin composition (D) comprises methacrylate-based resin (A), the graft copolymer (B) containing rubber and the graft copolymer (C) containing rubber
Methacrylate-based resin (A):
By by methacrylic ester 50 ~ 100 % by weight and the methacrylate-based resin that can carry out being polymerized with at least 1 of its copolymerization kind of monomer 0 ~ 50 % by weight and obtain;
Graft copolymer (B) containing rubber:
It is the graft copolymer containing rubber that monomer component (B-1), (B-2), (B-3), (B-4) are carried out being polymerized according to this order and formed, median size wherein as the rubber particles of the polymkeric substance of monomer component (B-1) and (B-2) is 0.2 ~ 0.4 μm
(B-1) by methacrylic ester (b-1-1) 60 ~ 100 % by weight, can with mono-functional's monomer (b-1-2) 40 ~ 0 % by weight of its copolymerization and the monomer component formed relative to the multi-functional monomer (b-1-3) that (b-1-1)+(b-1-2) 100 weight part is 0.05 ~ 10 weight part
(B-2) by acrylate (b-2-1) 50 ~ 100 % by weight, can with mono-functional's monomer (b-2-2) 50 ~ 0 % by weight of its copolymerization and the monomer component formed relative to the multi-functional monomer (b-2-3) that (b-2-1)+(b-2-2) 100 weight part is 0.05 ~ 10 weight part
(B-3) by methacrylic ester (b-3-1) 50 ~ 100 % by weight and the monomer component that can form with mono-functional's monomer (b-3-2) 50 ~ 0 % by weight of its copolymerization,
(B-4) by methacrylic ester (b-4-1) 0 ~ 70 % by weight and the monomer component that can form with mono-functional's monomer (b-4-2) 100 ~ 30 % by weight of its copolymerization;
Graft copolymer (C) containing rubber:
It is the 2 Rotating fields polymkeric substance that monomer component (C-1), (C-2) are carried out being polymerized according to this order and formed, and the median size wherein as the rubber particles of the polymkeric substance of monomer component (C-1) is 0.02 ~ 0.15 μm,
(C-1) by acrylate (c-1-1) 50 ~ 100 % by weight, methacrylic ester (c-1-2) 50 ~ 0 % by weight and the monomer component that forms relative to the multi-functional monomer (c-1-3) that (c-1-1)+(c-1-2) 100 weight part is 0.05 ~ 10 weight part
(C-2) by methacrylic ester (c-2-1) 50 ~ 100 % by weight and the monomer component that can form with mono-functional's monomer (c-2-2) 50 ~ 0 % by weight of its copolymerization.
In acrylic resin film of the present invention, when to set methacrylic resin composition (D) be 100 weight part, the preferred acrylic resin film rubber particles contained as the polymkeric substance of monomer component (B-1) and (B-2) is 1 ~ 20 weight part, be 1 ~ 50 weight part as the rubber particles of the polymkeric substance of monomer component (C-1).
In acrylic resin film of the present invention, preferred monomers composition (C-1) meets formula (1),
20d≤w≤125d(1)
D: the median size (μm) being the rubber particles of the polymkeric substance as monomer component (C-1),
W: the parts by weight (relative to (c-1-1)+(c-1-2) 100 weight part) being multi-functional monomer (c-1-3).
Acrylic resin film of the present invention, the thickness of preferred film is 30 ~ 500 μm.
Acrylic resin film of the present invention, preferably its at least 1 surface has coating.
In addition, acrylic resin film of the present invention, preferred one surface has hard coat, and its contrary face has undercoat.
At least one be selected from urethane acrylate resinoid, acrylic resin and silicone based resin is preferably cured and is formed by described hard coat.
The surface hardness of described hard coat is preferably more than HB.
The present invention also can be the moulded products utilizing above-mentioned acrylic resin film to manufacture.
Acrylic resin film of the present invention is stacked on base material and is formed by laminated product of the present invention.
Invention effect
The bend-resistance albefaction of acrylic resin film of the present invention is excellent, surface hardness also high, fracture-resistant is excellent, the transparency is excellent.
Embodiment
For the graft copolymer (B) containing rubber of the present invention, first monomer component (B-1) carried out being polymerized and obtain innermost layer polymkeric substance.The monomer component (B-1) used in the present invention by methacrylic ester (b-1-1) 60 ~ 100 % by weight, can form with mono-functional's monomer (b-1-2) 40 ~ 0 % by weight of its copolymerization and polyfunctional monomer (b-1-3) 0.05 ~ 10 weight part (relative to (b-1-1)+(b-1-2) 100 weight part).The polymerization of monomer component (B-1), can be undertaken mixing rear use by whole monomer, also monomer composition can be carried out changing and use with more than 2 sections in addition.
As methacrylic ester (b-1-1) preferable methyl alkyl acrylate used here.From the viewpoint of polymerizability and cost, preferred alkyl to be carbonatoms be 1 ~ 12 alkyl, it can be straight-chain also can be branched.As its concrete example, include, for example: methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, 2-Ethylhexyl Methacrylate, Octyl methacrylate, Methacrylamide, methacrylic acid beta-hydroxy ethyl ester, dimethylaminoethyl methacrylate, glycidyl methacrylate etc., these monomers above-mentioned may be combined with two or more and use.Relative to the total amount of (b-1-1) and (b-1-2), methacrylic ester (b-1-1) proportion preferably 60 ~ 100 % by weight, more preferably 70 ~ 100 % by weight, most preferably 80 ~ 100 % by weight.During owing to being less than 60 % by weight, surface hardness, the transparency deterioration of film, therefore not preferred.
In addition, as required, also can make methacrylic ester (b-1-1) and mono-functional's monomer (b-1-2) of copolymerization can carry out copolymerization.As above-mentioned these can the vinyl unsaturated monomer of copolymerization, include, for example acrylate, preferred alkyl acrylate.From polymerisation reactivity and cost aspect, preferred alkyl to be carbonatoms be 1 ~ 12 alkyl, it can be straight-chain also can be branched.As its concrete example, include, for example: methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-EHA, n-octyl, propenoic acid beta-hydroxy base ethyl ester, acrylate, glycidyl acrylate, acrylamide, N hydroxymethyl acrylamide etc.In addition, vinyl unsaturated monomer as other can be enumerated: vinylchlorid, the vinyl halides such as bromine ethene, vinyl cyanide, the vinyl cyanides such as methacrylonitrile, vinyl formate, vinyl-acetic ester, the vinyl acetate such as propionate, vinylbenzene, Vinyl toluene, the aromatic vinyl analog derivatives such as alpha-methyl styrene, vinylidene chloride, the sub-ethene of the halos such as vinylidene, vinylformic acid, sodium acrylate, the vinylformic acid such as calcium acrylate and salt thereof, methacrylic acid, sodium methacrylate, methacrylic acid and the salt etc. thereof such as methacrylic acid calcium, these monomers above-mentioned may be combined with two or more and use.
The multi-functional monomer (b-1-3) that every 1 molecule due to the graft inter polymer (B) containing rubber has more than 2 unconjugated reactive double bonds has carried out copolymerization, and therefore, the polymkeric substance obtained becomes crosslinked.Can enumerate as multi-functional monomer (b-1-3) used here: allyl methacrylate(AMA), allyl acrylate, triallyl cyanurate, triallyl isocyanurate, Phthalic acid, diallyl ester, diallyl maleate, hexanodioic acid divinyl ester, Vinylstyrene ethylene glycol dimethacrylate, Vinylstyrene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, trimethylolpropane trimethacrylate, Viscoat 295, pentaerythritol tetramethylacrylate, tetramethylol methane tetraacrylate, glycol dimethacrylate and dipropylene etc., above-mentioned these can use in combination of two or more.
Relative to addition preferably 0.05 ~ 10 weight part of the multi-functional monomer (b-1-3) in (b-1-1)+(b-1-2) 100 weight parts monomers composition (B-1), more preferably 0.1 ~ 10 weight part.When the addition of multi-functional monomer is less than 0.05 weight part, have the tendency that can not form crosslinked, and when being greater than 10 weight fraction, the fracture-resistant of film there is the tendency of reduction.
Then, under the existence of innermost layer polymkeric substance (polymkeric substance of (B-1)), make monomer component (B-2) be polymerized, then obtain rubber particles.The monomer component (B-2) used in the present invention, for comprising acrylate (b-2-1) 50 ~ 100 % by weight, can carry out mono-functional's monomer (b-2-2) 50 ~ 0 % by weight of copolymerization and the monomer component of multi-functional monomer (b-2-3) 0.05 ~ 10 weight part (relative to (b-2-1)+(b-2-2) 100 weight part) with it.The polymerization of monomer component (B-2), also can use whole monomer mixing, also monomer composition can be carried out changing and use with more than 2 sections in addition.
As acrylate (b-2-1) used here, preferred alkyl acrylate.From the view point of polymerisation reactivity and cost, preferred alkyl to be carbonatoms be 1 ~ 12 alkyl, it can be straight-chain also can be branched.As its concrete example, include, for example: methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-EHA, n-octyl, propenoic acid beta-hydroxy base ethyl ester, acrylate, glycidyl acrylate, acrylamide, N hydroxymethyl acrylamide etc.These monomers above-mentioned can use a kind or combine two or more use.Relative to the total amount of (b-2-1) and (b-2-2), the ratio shared by acrylate (b-2-1) preferably 50 ~ 100 % by weight, more preferably 60 ~ 100 % by weight, most preferably 70 ~ 100 % by weight.When being less than 50 % by weight, the fracture-resistant of film worsens, therefore not preferred.
In addition, as required, also can make acrylate (b-2-1) and mono-functional's monomer (b-2-2) of copolymerization can carry out copolymerization.As above-mentioned these can the vinyl unsaturated monomer of copolymerization, include, for example methacrylic ester, preferable methyl alkyl acrylate.From the view point of polymerisation reactivity and cost, preferred alkyl to be carbon atom be 1 ~ 12 alkyl, and it can be straight-chain also can be branched.As its concrete example, include, for example: methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, 2-Ethylhexyl Methacrylate, Octyl acrylate, Methacrylamide, methacrylic acid beta-hydroxy ethyl ester, dimethylaminoethyl methacrylate, glycidyl methacrylate etc.In addition, vinyl unsaturated monomer as other can be enumerated: vinylchlorid, the vinyl halides such as bromine ethene, vinyl cyanide, the vinyl cyanides such as methacrylonitrile, vinyl formate, vinyl-acetic ester, the vinyl acetate such as propionate, vinylbenzene, Vinyl toluene, the aromatic vinyl derivatives such as alpha-methyl styrene, vinylidene chloride, the sub-ethene of the halos such as vinylidene, vinylformic acid, sodium acrylate, the vinylformic acid such as calcium acrylate and salt thereof, methacrylic acid, sodium methacrylate, methacrylic acid and the salt etc. thereof such as methacrylic acid calcium, these monomers above-mentioned may be combined with two or more and use.
With regard to the graft inter polymer (B) containing rubber, the multi-functional monomer (b-2-3) due to every 1 molecule with the unconjugated reactive double bond of more than 2 has carried out copolymerization, and therefore, the polymkeric substance obtained becomes crosslinked.Can enumerate as multi-functional monomer (b-2-3) used here: allyl methacrylate(AMA), allyl acrylate, triallyl cyanurate, triallyl isocyanurate, Phthalic acid, diallyl ester, diallyl maleate, hexanodioic acid divinyl ester, Vinylstyrene ethylene glycol dimethacrylate, Vinylstyrene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, trimethylolpropane trimethacrylate, Viscoat 295, pentaerythritol tetramethylacrylate, tetramethylol methane tetraacrylate, dipropyl glycol dimethacrylate and dipropyl glycol diacrylate etc., above-mentioned these also can use in combination of two or more.
Relative to (b-2-1)+(b-2-2) 100 weight part, addition preferably 0.05 ~ 10 weight part of the multi-functional monomer (b-2-3) in monomer component (B-2), more preferably 0.1 ~ 10 weight part.When the addition of multi-functional monomer is less than 0.05 weight part, have the tendency that can not form crosslinked, and when being greater than 10 weight fraction, the fracture-resistant of film there is the tendency of reduction.
Then, under the existence of rubber particles (polymkeric substance of (B-1)+(B-2)), make monomer component (B-3) carry out being polymerized and obtaining graft copolymer.The monomer component (B-3) used in the present invention is made up of methacrylic ester (b-3-1) 50 ~ 100 % by weight, the monomer component of mono-functional's monomer (b-3-2) 50 ~ 0 % by weight that can carry out copolymerization with it.In the polymerization of monomer component (B-3), whole monomer mixing can be used, also monomer composition can be changed and use with more than 2 sections in addition.
As methacrylic ester (b-3-1) used here, preferable methyl alkyl acrylate.From polymerisation reactivity and cost aspect, preferred alkyl to be carbonatoms be 1 ~ 12 alkyl, and it can be straight-chain also can be branched.As its concrete example, include, for example: methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, 2-Ethylhexyl Methacrylate, Octyl methacrylate, Methacrylamide, methacrylic acid beta-hydroxy ethyl ester, dimethylaminoethyl methacrylate, glycidyl methacrylate etc., these monomers above-mentioned also can use in combination of two or more.Relative to the total amount of (b-3-1) and (b-3-2), methacrylic ester (b-3-1) proportion preferably 50 ~ 100 % by weight, more preferably 70 ~ 100 % by weight, most preferably 80 ~ 100 % by weight.During owing to being less than 50 % by weight, surface hardness, the transparency deterioration of film, therefore not preferred.
In addition, as required, also can make methacrylic ester (b-3-1) and mono-functional's monomer (b-3-2) of copolymerization can carry out copolymerization.As above-mentioned these can the vinyl unsaturated monomer of copolymerization, include, for example acrylate, preferred alkyl acrylate.From polymerisation reactivity and cost aspect, preferred alkyl to be carbonatoms be 1 ~ 12 alkyl, and it can be straight-chain also can be branched.As its concrete example, include, for example: methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-EHA, n-octyl, propenoic acid beta-hydroxy base ethyl ester, acrylate, glycidyl acrylate, acrylamide, N hydroxymethyl acrylamide etc.In addition, vinyl unsaturated monomer as other can be enumerated: vinylchlorid, the vinyl halides such as bromine ethene, vinyl cyanide, the vinyl cyanides such as methacrylonitrile, vinyl formate, vinyl-acetic ester, the vinyl acetate such as propionate, vinylbenzene, Vinyl toluene, the aromatic vinyl derivatives such as alpha-methyl styrene, vinylidene chloride, the sub-ethene of the halos such as vinylidene, vinylformic acid, sodium acrylate, the vinylformic acid such as calcium acrylate and salt thereof, methacrylic acid, sodium methacrylate, methacrylic acid and the salt etc. thereof such as methacrylic acid calcium, these monomers above-mentioned also can use in combination of two or more.
It should be noted that, monomer component (B-3) is not containing the composition of multi-functional monomer.
Then, under the existence of graft copolymer (polymkeric substance of (B-1)+(B-2)+(B-3)), monomer component (B-4) is made to carry out being polymerized the graft copolymer (B) obtained containing rubber.The monomer component (B-4) used in the present invention is made up of methacrylic ester (b-4-1) 0 ~ 70 % by weight, mono-functional's monomer (b-4-2) 100 ~ 30 % by weight that can carry out copolymerization with it.But the composition of monomer component (B-4) is different from the composition of above-mentioned monomer component (B-3).In the polymerization of monomer component (B-4), also the mixing of whole monomer can be used, also monomer composition can be carried out changing in addition and use with more than 2 sections.
As methacrylic ester (b-4-1) used here, preferable methyl alkyl acrylate.From polymerizability and cost aspect, preferred alkyl to be carbonatoms be 1 ~ 12 alkyl, and it can be straight-chain also can be branched.As its concrete example, include, for example: methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, 2-Ethylhexyl Methacrylate, Octyl acrylate, Methacrylamide, methacrylic acid beta-hydroxy ethyl ester, dimethylaminoethyl methacrylate, glycidyl methacrylate etc., and these monomers above-mentioned also can use in combination of two or more.Relative to the total amount of (b-4-1) and (b-4-2), methacrylic ester (b-4-1) proportion preferably 0 ~ 70 % by weight, more preferably 20 ~ 70 % by weight, most preferably 30 ~ 70 % by weight.If become micro mist to when latex carries out powdered after polymerization when being greater than 70 % by weight, dispersedly time shaping in addition to worsen, therefore transparency deterioration, thus not preferred.
In addition, as required, also can by methacrylic ester (b-4-1) with mono-functional's monomer (b-4-2) of copolymerization can carry out copolymerization.As above-mentioned these can the vinyl unsaturated monomer of copolymerization, include, for example acrylate, and preferred alkyl acrylate.From polymerisation reactivity and cost aspect, preferred alkyl to be carbonatoms be 1 ~ 12 alkyl, and it can be straight-chain also can be branched.As its concrete example, include, for example: methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-EHA, n-octyl, propenoic acid beta-hydroxy base ethyl ester, acrylate, glycidyl acrylate, acrylamide, N hydroxymethyl acrylamide etc.In addition, vinyl unsaturated monomer as other can be enumerated: vinylchlorid, the vinyl halides such as bromine ethene, vinyl cyanide, the vinyl cyanides such as methacrylonitrile, vinyl formate, vinyl-acetic ester, the vinyl acetate such as propionate, vinylbenzene, Vinyl toluene, the aromatic vinyl derivatives such as alpha-methyl styrene, vinylidene chloride, the sub-ethene of the halos such as vinylidene, vinylformic acid, sodium acrylate, the vinylformic acid such as calcium acrylate and salt thereof, methacrylic acid, sodium methacrylate, methacrylic acid and the salt etc. thereof such as methacrylic acid calcium, these monomers above-mentioned can use in combination of two or more.
It should be noted that, monomer component (B-4) is the composition not containing multi-functional monomer.
In the total amount ((B-1)+(B-2)+(B-3)+(B-4)) 100 % by weight of monomer component (B-1) ~ (B-4), monomer component (B-1) proportion preferably 5 ~ 40 % by weight, more preferably 10 ~ 30 % by weight.When being greater than 40 % by weight, the fracture-resistant of film reduces sometimes.In the total amount 100 % by weight of monomer component (B-1) ~ (B-4), monomer component (B-2) proportion preferably 20 ~ 70 % by weight, more preferably 30 ~ 60 % by weight.When being greater than 70 % by weight, the surface hardness of film reduces sometimes.In the total amount 100 % by weight of monomer component (B-1) ~ (B-4), monomer component (B-3) proportion preferably 5 ~ 40 % by weight, more preferably 10 ~ 30 % by weight.When being greater than 40 % by weight, the fracture-resistant of film reduces sometimes.In the total amount 100 % by weight of monomer component (B-1) ~ (B-4), monomer component (B-4) proportion preferably 1 ~ 40 % by weight, more preferably 5 ~ 30 % by weight.When being greater than 40 % by weight, the surface hardness of film reduces sometimes.
For the graft inter polymer (C) containing rubber of the present invention, first obtain rubber particles by the polymerization of monomer component (C-1).The monomer component (C-1) used in the present invention comprises acrylate (c-1-1) 50 ~ 100 % by weight, methacrylic ester (c-1-2) 50 ~ 0 % by weight and multi-functional monomer (c-1-3) 0.05 ~ 10 weight part (relative to (c-1-1)+(c-1-2) 100 weight part).In the polymerization of monomer component (C-1), whole monomer can be carried out mixing and use, also monomer composition can be carried out changing using with more than 2 sections in addition.Here used acrylate (c-1-1) and methacrylic ester (c-1-2), can use the material used during the polymerization with the graft copolymer (B) containing rubber identical.Relative to the total amount of (c-1-1) and (c-1-2), acrylate (c-1-1) proportion preferably 50 ~ 100 % by weight, more preferably 60 ~ 100 % by weight, most preferably 70 ~ 100 % by weight.When being less than 50 % by weight, the fracture-resistant of film worsens, therefore not preferred.
Then, under the existence of rubber particles (polymkeric substance of (C-1)), make monomer component (C-2) carry out being polymerized the graft copolymer (C) obtained containing rubber.The monomer component (C-2) used in the present invention is made up of methacrylic ester (c-2-1) 50 ~ 100 % by weight, mono-functional's monomer (c-2-2) 50 ~ 0 % by weight that can carry out copolymerization with it.Methacrylic ester used herein (c-2-1) and acrylate (c-2-2) can use the material used during the polymerization with the graft copolymer (B) containing rubber identical.Relative to the total amount of (c-2-1) and (c-2-2), acrylate (c-2-1) proportion preferably 50 ~ 100 % by weight, more preferably 60 ~ 100 % by weight, most preferably 70 ~ 100 % by weight.When being less than 50 % by weight, surface hardness, the transparency deterioration of film, therefore not preferred.
In the graft copolymer (C) containing rubber, in the total amount ((C-1)+(C-2)) 100 % by weight of monomer component (C-1) and (C-2), monomer component (C-1) proportion preferably 10 ~ 60 % by weight, more preferably 20 ~ 50 % by weight.When being less than 10 % by weight, fracture-resistant reduces sometimes.
For methacrylate-based resin of the present invention (A), be by making methacrylic ester 50 ~ 100 % by weight and at least a kind of monomer 0 ~ 50 % by weight that can carry out copolymerization with it carry out being polymerized and obtain.Methacrylic ester and mono-functional's monomer that can carry out copolymerization with it, can use the monomer used when being polymerized with the graft copolymer (B) containing rubber identical.The ratio shared in methacrylate-based resin (A) entirety of methacrylic ester preferably 50 ~ 100 % by weight, more preferably 60 ~ 100 % by weight, most preferably 70 ~ 100 % by weight.When being less than 50 % by weight, surface hardness, the transparency deterioration of film, therefore not preferred.
The manufacture method of the methacrylate-based resin (A) in the present invention, the graft copolymer (B) containing rubber and the graft copolymer (C) containing rubber is not particularly limited, and can use known emulsion polymerization, emulsion-suspension polymerization, suspension polymerization, mass polymerization or solution polymerization process.To the graft copolymer (B) containing rubber and the polymerization of graft copolymer (C) containing rubber, particularly preferably emulsion polymerization.
Because by the latex that emulsion polymerization obtains, therefore by commonly solidifying, cleaning and the operation of drying, or, by adopting the process of spraying dry, lyophilize etc., resin combination is carried out be separated, reclaim.
The median size preferably 0.2 ~ 0.4 μm of the rubber particles of the contained polymkeric substance as monomer component (B-1) and (B-2) in graft copolymer (B) containing rubber, more preferably 0.2 ~ 0.3 μm.When being less than 0.2 μm, fracture-resistant worsens, therefore preferred, and when being greater than 0.4 μm, bend-resistance albefaction, the transparency reduce, therefore not preferred.
The median size preferably 0.02 ~ 0.15 μm of the rubber particles of the polymkeric substance as monomer component (C-1) contained in the graft copolymer (C) containing rubber, more preferably 0.02 ~ 0.13 μm, preferably 0.03 ~ 0.10 μm further.When being less than 0.02 μm, fracture-resistant worsens, therefore preferred, and when being greater than 0.15 μm, bend-resistance albefaction, the transparency reduce, therefore not preferred.
The amount of the multi-functional monomer (c-1-3) of the graft copolymer (C) containing rubber, relevant to the median size of the rubber particles of the polymkeric substance as monomer component (C-1), considerable influence is produced to the resistance to bending albefaction of film.That is, the median size d (μm) of rubber particles and the parts by weight w (relative to (c-1-1)+(c-1-2) 100 weight part) of multi-functional monomer (c-1-3) meets following formula (1) is very important.
20d≤w≤125d(1)
The preferred scope as shown in the above formula of parts by weight of multi-functional monomer, time beyond this scope, resistance to bending albefaction worsens, therefore not preferred.
Methacrylic resin composition (D) in the present invention comprises methacrylate-based resin (A), the graft copolymer (B) containing rubber and the graft copolymer (C) containing rubber, and using the graft copolymer containing rubber comprising two types as feature.The fracture-resistant of membrane is showed by the graft copolymer (B) of the rubber containing rubber size being 0.2 μm ~ 0.4 μm.Bend-resistance albefaction is shown by the graft copolymer (C) of the rubber containing rubber size being 0.02 μm ~ 0.15 μm.The content of the graft copolymer (B) containing rubber, when methacrylic resin composition (D) is set to 100 weight part, its rubber particles content preferably 1 ~ 20 weight part, further preferred 1 ~ 15 weight part.The fracture-resistant being less than film during 1 weight part worsens, and when being greater than 20 weight part, the surface hardness of film, the transparency, bend-resistance albefaction worsen.The content of the graft copolymer (C) containing rubber, when methacrylic resin composition (D) is set to 100 weight part, its rubber particles content preferably 1 ~ 50 weight part, further preferred 1 ~ 35 weight part.The fracture-resistant being less than film during 1 weight part worsens, and surface hardness, the transparency deterioration of film when being greater than 50 weight part.
Methacrylic resin composition of the present invention (D) is particularly useful as film, such as, by as the extrusion and blow molding method of common extrusion by melting, T-shaped extrusion or rolling-molding method, also have sol-vent cast method etc., then can carry out processing film forming well.In addition, as required, when carrying out film and being shaping, contact (clamping) with roller or metal strip by making film two sides simultaneously, particularly by contacting with the roller of temperature or metal strip that are heated to more than second-order transition temperature, then can obtain the more excellent film of superficiality simultaneously.In addition, according to object, also can be the modification by the laminated forming of film, the film of two-way stretch.
In addition, in methacrylic resin composition of the present invention (D), as required, poly-glutarimide, Pyroglutaric acid polymkeric substance, lactone cyclization methacrylic resin, methacrylic resin, pet resin, polybutylene terephthalate resin etc. can also be coordinated.Method for mixing is not particularly limited, and can utilize known method.
In methacrylic resin composition of the present invention (D), mineral-type pigment or organic dyestuff can be added in order to paint, separately or can be combined two or more to the stability of light and heat add antioxidant, thermo-stabilizer, UV light absorber, ultra-violet stabilizer etc. to improve further, or separately or combine that two or more interpolation is antibacterial, reodorant, lubricant etc.
The thickness of acrylic resin film of the present invention preferably 30 ~ 500 μm, more preferably 30 ~ 400 μm.When the thickness of film is less than 30 μm, the processibility of film has the tendency of reduction, and during more than 500 μm, the formability of film has the tendency of reduction.
In addition, acrylic resin film of the present invention, as required, reduces the gloss on film surface by known method.Such as, can be implemented by the method etc. to mixing inorganic filler in methacrylic resin composition (D) or bridging property polymer particles.In addition, the film obtained is reduced to the gloss on film surface by carrying out embossing processing.
Acrylic resin film of the present invention, also can be using this film as base material, and arrange the form of coating at least one surface thereof.About kind and the formation of coating, function (such as, the raising of surface hardness and scuff resistance, certainly healing property, anti-dazzle function, anti-reflective function, anti-fingerprint attached function etc.) as required can at random be selected, and there is no particular restriction.Preferred setting has the coating of at least one be selected from urethane acrylate resinoid, acrylic resin and silicone based resin.Surface hardness is improved further while the fracture-resistant that can have in maintenance acrylic resin film of the present invention thus, resistance to bending albefaction.
Following coating can be used: UnidicV-6840 as the coating for the formation of coating, UnidicV-6841, UnidicWHV-649, UnidicEKS-675, UnidicEKC-1054, Unidic-124, UnidicEKC-821, UnidicRC29-120, UnidicEKC-578 (DIC system), BeamSET1200, BeamSET371, BeamSET710, BeamSET575 (Arakawa Chemical Industries, Ltd.'s system), RushifuraruG-720, RushifuraruG-2000, RushifuraruNAG-1000, RushifuraruNAG-3000, RushifuraruNEH-1000, RushifuraruNEH-2000 (Japanese paint Co., Ltd. system), AicaaitronZ606-25, AicatronZ606-76, AicatronZ606-77, AicatronZ606-78, AicatronZ880-4, AicatronZ-883 (AICA Industrial Co., Ltd system) etc.
The formation of coating can utilize known method to implement, but forms coating preferably by print process or coating method.In this situation, the coating fluid (solution or dispersion liquid) of modulation in order to form coating, by coating solution at least one side of acrylic resin film, in order to carry out heat drying except desolventizing, can it be made to solidify by the irradiation of electron beam, ultraviolet, gamma-rays etc. thus form the tunicle (hard coat) of solid as required.The method due to the adaptation of coating and acrylic resin film good therefore preferred.Usual illuminate condition should be determined according to the light solidified of coating, but irradiation dose, be generally 300 ~ 10000mJ/cm
2left and right.
As print process, include, for example, the known print processes such as gravure processes, screen painting method, flexographic printing process.
As coating method, include, for example: flow coat method, spraying method, bar formula coating method (barcoating), photogravure coating method, photogravure rod coating method, reverse kiss are coated with method (kissreversecoating), micro-gravure coating process, rolling method, scraper plate coating method, stick coating method (rodcoating), gluing rolling method, air knife coating method, comma coating method, inverse roller coating method, material transfer rolling method, lick the known coating processes such as paint roller coating method, curtain stream coating method, Dipcoat method.
Preferably there is the solvent of following characteristic: acrylic resin and/or urethane acrylate resinoid and/or silicone based resin can be carried out dissolving or disperseing equably as solvent; And practical huge detrimentally affect can not be produced to the physical property of acrylic resin film (physical strength, the transparency etc.); Have not higher than the second-order transition temperature more than 80 DEG C of acrylic resin film further, preferably not higher than volatile solvent of the boiling point of the second-order transition temperature more than 30 DEG C of acrylic resin film.
Methyl alcohol can be enumerated as solvent, ethanol, Virahol, propyl carbinol, the alcoholic solvents such as ethylene glycol, dimethylbenzene, toluene, the aromatic series kind solvents such as benzene, hexane, the Aliphatic hydrocarbon solvents such as pentane, chloroform, the halogenated hydrocarbon solvents such as tetracol phenixin, phenol, the phenol solvents such as cresols, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), acetone, the ketones solvents such as pimelinketone, Anaesthetie Ether, to toluene methyl ether, 1,2-glycol dimethyl ether, 1,2-dibutoxy ethane, 1,1-Methylal(dimethoxymethane), 1,1-glycol dimethyl ether, Isosorbide-5-Nitrae-dioxane, the ether solvents such as tetrahydrofuran (THF) (THF), formic acid, acetic acid, the fatty acid solvents such as propionic acid, the anhydrides solvents such as acetic anhydride, ethyl acetate, n-propyl acetate, butylacetate, the esters solvents such as butyl formate, ethamine, Tolylamine, dimethyl formamide, the nitrogen-containing solvents such as N,N-DIMETHYLACETAMIDE, thiophene, the sulfur-bearing solvents such as dimethyl sulfoxide (DMSO), Pyranton, 2-methyl cellosolve (methylcyclohexane), cellosolvo (ethyl cellosolve), dibutoxy ethanol (ethylene glycol butyl ether), glycol ether, 2-monoethanolamine, acetyl cyanalcohol, diethanolamine, morpholine, 1-acetoxyl-2-Ethoxyethane, 2-acetoxyl-1-methoxy propane etc. has the solvent of two or more functional group, water etc., various known solvent.These materials can be used alone or combine two or more and use above.
The physical property that can alleviate due to the solvent that is principal constituent with ethyl acetate, n-propyl acetate, isopropyl alcohol, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) the acrylic resin film caused because of solvent in above-mentioned substance reduces, therefore preferably.In addition, from the view point of the adaptation of coating and acrylic resin film, preferably combination uses N-BUTYL ACETATE and methyl iso-butyl ketone (MIBK).In addition, the gloss uneven after coating, preferably combination uses the high boiling solvent such as solvent, 2-acetoxyl-1-methoxy propane, pimelinketone of the medium boiling point of butylacetate, methyl iso-butyl ketone (MIBK) etc.
What occur from the view point of the alleviating of coating fluid holiday, doctor line alleviates, and is preferably carried out filtering by coating fluid and is removed by foreign matter.Can implement to filter after coating fluid modulation, also can implement before the coating to filter or limit is carried out painting selvedge and filtered.Filter by known filtration unit, but the CPII-10 preferably using such as JNCfilter (strain) to make, 03,01 (trade(brand)name).
The thickness of coating preferably 1 ~ 20 μm, more preferably 1 ~ 10 μm, most preferably 3 ~ 7 μm.During more than 20 μm, film easily breaks, and when being less than 1 μm, surface hardness reduces.
Acrylic resin film of the present invention can have undercoat on the opposing face in face arranging hard coat.The ink used in the printing carried out in post-treatment operation, resin that the metal adaptation used in metal evaporation is good can be used in as the composition of undercoat.Such as can use polyurethane based resin, acrylic resin, polyester resin, polycarbonate, redix, trimeric cyanamide resinoid.
The thickness of undercoat preferably 0.5 ~ 10 μm, more preferably 0.5 ~ 5 μm, most preferably 0.5 ~ 3 μm.Little to the contribution of adaptation when coat-thickness is less than 0.5 μm, and there is crackle when vacuum forming when being greater than 10 μm.
Acrylic resin film of the present invention can be carried out lamination and use on the base material such as metal, plastics.Laminating method as film can be enumerated: on the metal sheet such as laminated forming or steel plate after coating adhesive, is placed on by film and metal sheet carries out drying thus carries out the wet type laminating of fitting and dry lamination method, extruding layer platen press, hot melt layer platen press etc.Can enumerate as by film lamination method on a plastic part: film is placed in metal die, by the insert molding of injection moulding potting resin or carry out Outshooting compression shaping, or be placed in metal die after film is carried out premolding, by injection moulding in the film of injection moulding potting resin etc.
Acrylic resin film of the present invention is laminated to the film laminated product that base material obtains, can be used for the application such as automobile interior trim material, automobile decorative material and substitute purposes, window frame, bath stop up the construction timbers such as equipment, wallpaper, flooring material, the cover of sundry goods product, furniture or electrical equipment, the cover of the OA equipment of facsimile recorder, notebook computer, duplicating machine etc., the front panel of the liquid crystal panel of the terminal of portable phone, intelligent acousimeter, tablet etc., and electrically or in the parts of electronic installation etc.In addition, as moulded products, can be used in lighting lens, automobile headlamp, optical lens, optical fiber, CD, liquid crystal light guiding plate, liquid crystal film, the necessary medical treatment product of sterilising treatment, high-frequency electronic food heating and regulating container, the cover of family's electrical article, toy or recreation product etc.
Embodiment
Below, based on embodiment, the present invention will be described in more detail, but the present invention is not limited to these embodiments.
In addition, " part " manufactured in row, embodiment and comparative example is weight part, and " % " represents % by weight.
Abbreviation represents following substances respectively.
BA: n-butyl acrylate
MMA: methyl methacrylate
St: vinylbenzene
AlMA: allyl methacrylate(AMA)
It should be noted that, each measuring method of the physical property measured in following embodiment and comparative example is as follows.
(evaluation of polymerisation conversion)
The polymeric latex obtained is carried out in hot air dryer at 120 DEG C drying in 1 hour and try to achieve solids component amount, calculate polymerisation conversion (%) by the monomer (%) of 100 × solids component amount/add.
(evaluation of the median size of rubber particles)
Graft copolymer (B) (or containing rubber graft copolymer (C)) containing rubber is carried out admixing with the ratio of 50:50 with SUMIPEXEX (Sumitomo Chemical Co's system) and the mixture that obtains carries out shaping and film that is that obtain, by transmission electron microscope (NEC JEM-1200EX), adopt acceleration voltage 80kV, RuO
4dyeing ultrathin sectioning is made a video recording, and selects arbitrarily 100 rubber particles portraits, try to achieve the mean value in the particle footpath of these rubber particles from the photo obtained.
(evaluation of mist degree)
The transparency of the film obtained take JISK6714 as benchmark, and be 23 ± 2 DEG C in temperature, and humidity is measure mist degree under the condition of 50% ± 5%.
(evaluation of pencil hardness)
The pencil hardness of gained film is measured according to JISK5600-5-4 benchmark.
(evaluation of fracture-resistant)
Film paper knife is cut off, carries out following evaluation.
Zero: cut surface does not confirm generation crackle
△: cut surface confirms and there occurs crackle
×: cut surface confirms and significantly there occurs crackle
(resistance to bending albefaction)
Film is carried out 180 degree of bendings at 23 DEG C, observes albefaction state and evaluate as follows.
Zero: do not confirm albefaction
△: confirm and only have a small amount of albefaction
×: albefaction is remarkable
(at 120 DEG C degree of drawing)
The thermostatic bath of 120 DEG C is installed, utilizes universal tensile testing machine, chuck spacing be 50mm, draw speed measures under being the condition of 200mm/min.When coating reaches the extension can not following acrylic resin film, mensuration coating there is extensibility during crackle.
(Production Example 1)
< contains the manufacture > of the graft inter polymer (B1) of rubber
The making of innermost layer polymkeric substance:
The mixture of following composition is placed in the reactor of glass, in stream of nitrogen gas after warming while stirring to 80 DEG C, add 25% in the mixed solution of monomer mixture (B-1) of Production Example 1 (in the table 1) and the tert-butyl hydroperoxide 0.1 part be made up of methyl methacrylate 25 parts, allyl methacrylate(AMA) 1 part once, carry out the polymerization of 45 minutes.
Then last 1 hour by remaining for this mixed solution 75% to add continuously.Add after terminating, keep at the same temperature completing polymerization in 2 hours.In addition, during this period in add 0.2 part of N-sodium lauroyl sareosine.The polymerisation conversion (polymerization growing amount/monomer add-on) of the innermost layer crosslinked methacrylic acids polymers latex obtained is 98%.
The making of rubber particles:
The innermost layer polymer latex obtained is kept 80 DEG C in stream of nitrogen gas, after adding Potassium Persulphate 0.1 part, the monomer mixture be made up of ((B-2) of the Production Example 1 in table 1) is lasted 5 hours added continuously n-butyl acrylate 41 parts, vinylbenzene 9 parts, allyl methacrylate(AMA) 1 part.Here potassium oleate 0.1 part point is added for three times.After monomer mixed solution interpolation terminates, add Potassium Persulphate 0.05 part again to complete polymerization and keep 2 hours.The polymerisation conversion of the rubber particles obtained is 99%.
The making of graft copolymer:
The rubber particles latex obtained is remained on 80 DEG C, after adding Potassium Persulphate 0.02 part, the monomer mixture ((B-3) of the Production Example 1 in table 1) of methyl methacrylate 14 parts, n-butyl acrylate 1 part is lasted 1 hour and has added continuously.Monomer mixed solution keeps obtaining graft copolymer latex in 1 hour after adding and terminating.Polymerisation conversion is 99%.
The making of the graft copolymer containing rubber:
The rubber particles latex obtained is remained on 80 DEG C, the monomer mixture ((B-4) of the Production Example B1 in table 1) of methyl methacrylate 5 parts, n-butyl acrylate 5 parts is lasted 0.5 hour and adds continuously.The graft copolymer latex obtained for 1 hour containing rubber is kept after terminating to add monomer mixed solution.Polymerisation conversion is 99%.
By obtain containing the graft copolymer latex of rubber undertaken saltouing by calcium chloride solidify, thermal treatment, drying, obtain the graft copolymer (B1) containing rubber of white powder.
(Production Example 2 ~ 4)
Change to except proportioning as shown in table 1 except by each monomer ratio of monomer component (B-1) ~ (B-4) in Production Example 1, and Production Example 1 similarly carries out operating graft copolymer (B2) ~ (B4) obtained containing rubber.
[table 1]
(Production Example 5)
< contains the manufacture > of the graft copolymer (C1) of rubber
Be accompanied with in the 8L poly-unit of stirrer, load following material.
After fully replacing make it in fact under the state of anaerobic with nitrogen in polymerization machine, interior temperature is set as 60 DEG C, n-butyl acrylate 27 parts, methyl methacrylate 3 parts, the monomer mixture of allyl methacrylate(AMA) 0.9 part composition and the mixed solution of cumene hydroperoxide 0.2 part are lasted 3 hours add continuously, add after terminating and proceed polymerization in 0.5 hour again, obtain rubber particles (polymkeric substance of (C-1)).Polymerisation conversion is 99.5%.
Then, after Sodium docusate 0.05 part is mixed into, interior temperature is set as 60 DEG C, n-butyl acrylate 7 parts, the monomer mixture of methyl methacrylate 63 parts composition and the mixed solution of cumene hydroperoxide 0.2 part are lasted 5 hours add continuously, continue polymerization in 1 hour again, obtain the graft copolymer latex containing rubber.Polymerization turnover ratio is 98.5%.The latex obtained saltoutd by calcium chloride, solidifies, wash, dry, obtain the graft copolymer (C1) containing rubber of white powder.
The median size of the rubber particles of the graft copolymer (C1) containing rubber is 0.08 μm.
(embodiment 1 ~ 7 and comparative example 1 ~ 5)
Pulverous graft copolymer (B) and (C) containing rubber obtained, coordinate with rubber particles number (part) as shown in table 3 respectively, and, utilize mixing machine ((strain) KAWATA system, SUPERFLOATER type SFC-50) by the multipolymer (B) containing rubber, and SUMIPEXEX (Sumitomo Chemical system (C), the methacrylate-based resin of methyl methacrylate 95 % by weight/methyl acrylate 5 % by weight) carry out blending in 3 minutes, its total amount is made to be 100 parts, then, utilize the single screw extrusion machine with the ventilation opening of 40 millimeters of (milli) φ, and set barrel zone temperature and be 240 DEG C and carry out melting mixing, and be granulated.The pellet obtained is utilized the 40 millimeters of φ forcing machines (NAKAMURA produces machine (strain) system, NEX040397) with T-shaped die head, carry out shaping at die temperature is 240 DEG C, obtain the film that thickness is 100 μm.
To using the various characteristics of powder and the film obtained to evaluate, its result is as shown in table 2.It should be noted that, the rubber particles number in table 2 is parts by weight when being 100 weight part with resin combination entirety.
[table 2]
(embodiment 8 ~ 13 and comparative example 5 ~ 8)
On the film obtained according to embodiment 5 ~ 7 and comparative example 1 ~ 3,5, utilize scraping article emulsion coating machine (#6 and #10) to be coated with RC29-124 (Dainippon Ink Chemicals's system), and applying solid constituent concentration is set as the resinoid dispersion liquid of the urethane acrylate of 30%.After coating, at 80 DEG C, carry out dry 1min and make solvent evaporates, irradiate the ultraviolet of 748.4mJ/min, form the coating that thickness is 4 μm or 7 μm.The film obtained is carried out to the evaluation of various characteristic, its result is as shown in table 3
[table 3]
Claims (10)
1. an acrylic resin film, it is the acrylic resin film of methacrylic resin composition (D) being carried out membranization and being formed, described methacrylic resin composition (D) comprises: methacrylate-based resin (A), the graft copolymer (B) containing rubber and the graft copolymer (C) containing rubber, wherein
Methacrylate-based resin (A) is: by making methacrylic ester 50 ~ 100 % by weight and can carrying out being polymerized the methacrylate-based resin obtained with at least 1 of its copolymerization kind of monomer 0 ~ 50 % by weight;
Graft copolymer (B) containing rubber is the graft copolymer containing rubber by monomer component (B-1), (B-2), (B-3), (B-4) are carried out being polymerized according to this order and formed, median size wherein as the rubber particles of the polymkeric substance of monomer component (B-1) and (B-2) is 0.2 ~ 0.4 μm
(B-1) by methacrylic ester (b-1-1) 60 ~ 100 % by weight, can with mono-functional's monomer (b-1-2) 40 ~ 0 % by weight of its copolymerization and the monomer component formed relative to the multi-functional monomer (b-1-3) that (b-1-1)+(b-1-2) 100 weight part is 0.05 ~ 10 weight part
(B-2) by acrylate (b-2-1) 50 ~ 100 % by weight, can with mono-functional's monomer (b-2-2) 50 ~ 0 % by weight of its copolymerization and the monomer component formed relative to the multi-functional monomer (b-2-3) that (b-2-1)+(b-2-2) 100 weight part is 0.05 ~ 10 weight part
(B-3) by methacrylic ester (b-3-1) 50 ~ 100 % by weight and the monomer component that can form with mono-functional's monomer (b-3-2) 50 ~ 0 % by weight of its copolymerization,
(B-4) by methacrylic ester (b-4-1) 0 ~ 70 % by weight and the monomer component that can form with mono-functional's monomer (b-4-2) 100 ~ 30 % by weight of its copolymerization;
The 2 Rotating fields polymkeric substance of graft copolymer (C) containing rubber for monomer component (C-1), (C-2) are carried out being polymerized according to this order and formed, median size wherein as the rubber particles of the polymkeric substance of monomer component (C-1) is 0.02 ~ 0.15 μm
(C-1) by acrylate (c-1-1) 50 ~ 100 % by weight, methacrylic ester (c-1-2) 50 ~ 0 % by weight and the monomer component that forms relative to the multi-functional monomer (c-1-3) that (c-1-1)+(c-1-2) 100 weight part is 0.05 ~ 10 weight part
(C-2) by methacrylic ester (c-2-1) 50 ~ 100 % by weight and the monomer component that can form with mono-functional's monomer (c-2-2) 50 ~ 0 % by weight of its copolymerization.
2. acrylic resin film according to claim 1, wherein, when being 100 weight part with methacrylic resin composition (D), containing rubber particles 1 ~ 20 weight part of polymkeric substance, rubber particles 1 ~ 50 weight part as the polymkeric substance of monomer component (C-1) as monomer component (B-1) and (B-2).
3. acrylic resin film according to claim 1 and 2, wherein, monomer component (C-1) meets formula (1),
20d≤w≤125d(1)
D: the median size (μm) being the rubber particles of the polymkeric substance as monomer component (C-1),
W: the parts by weight relative to (c-1-1)+(c-1-2) 100 weight part being multi-functional monomer (c-1-3).
4. acrylic resin film according to claim 1 and 2, wherein, the thickness of this film is 30 ~ 500 μm.
5. acrylic resin film according to claim 1 and 2, wherein, at least 1 surface has coating.
6. acrylic resin film according to claim 1 and 2, wherein, has hard coat on a surface, and have undercoat on contrary face.
7. acrylic resin film according to claim 6, wherein, at least one resin be selected from urethane acrylate resinoid, acrylic resin and silicone based resin is cured and is formed by hard coat.
8. acrylic resin film according to claim 6, wherein, the surface hardness of hard coat is more than HB.
9. a products formed, it is formed by the acrylic resin film manufacture described in any one in claim 1 ~ 8.
10. a laminate, it is that acrylic resin film described in any one in base material superimposed layer claim 1 ~ 8 forms.
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| JP2011221425 | 2011-10-05 | ||
| JP2011-221425 | 2011-10-05 | ||
| PCT/JP2012/006309 WO2013051239A1 (en) | 2011-10-05 | 2012-10-02 | Acrylic resin film having excellent resistance to whitening on bending and excellent cracking resistance |
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| EP (1) | EP2765161B1 (en) |
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| CN105121543B (en) * | 2013-04-12 | 2018-01-26 | 株式会社可乐丽 | acrylic resin film |
| JP6459367B2 (en) * | 2014-10-02 | 2019-01-30 | ユーエムジー・エービーエス株式会社 | Thermoplastic resin composition and molded article thereof |
| WO2017115800A1 (en) * | 2015-12-28 | 2017-07-06 | 株式会社クラレ | Resin film |
| JP7219753B2 (en) * | 2018-03-22 | 2023-02-08 | 株式会社カネカ | ACRYLIC RESIN FILM, LAMINATED FILM, LAMINATED FILM MANUFACTURING METHOD, AND MOLDED PRODUCT |
| EP3831600B1 (en) * | 2018-07-27 | 2024-10-23 | Kuraray Co., Ltd. | Infrared light shielding multilayer sheet and method for producing same |
| JP6884271B2 (en) * | 2019-02-28 | 2021-06-09 | バンドー化学株式会社 | Makeup film |
| WO2021132557A1 (en) | 2019-12-27 | 2021-07-01 | 株式会社クラレ | Methacrylic resin composition |
| KR102693912B1 (en) * | 2020-07-20 | 2024-08-12 | 주식회사 엘지화학 | Thermoplastic resin and method for preparing the same |
| US20220403153A1 (en) * | 2020-07-20 | 2022-12-22 | Lg Chem, Ltd. | Thermoplastic resin and method of preparing the same |
| JP2022032164A (en) * | 2020-08-11 | 2022-02-25 | 藤森工業株式会社 | (meth)acrylic resin composition and (meth)acrylic resin film |
| JPWO2022137768A1 (en) | 2020-12-25 | 2022-06-30 | ||
| CN113278117B (en) * | 2021-05-25 | 2023-03-17 | 四川兴彩高新材料有限公司 | ASA resin, ASA non-folding white film and preparation method thereof |
| CN113278116B (en) * | 2021-05-25 | 2023-03-17 | 四川兴彩高新材料有限公司 | ASA non-breaking white high-rubber powder, ASA non-breaking white film and preparation method thereof |
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| WO2013051239A1 (en) | 2013-04-11 |
| TW201319152A (en) | 2013-05-16 |
| KR20140034929A (en) | 2014-03-20 |
| TWI478977B (en) | 2015-04-01 |
| KR101570049B1 (en) | 2015-11-19 |
| US10253175B2 (en) | 2019-04-09 |
| EP2765161B1 (en) | 2018-11-28 |
| JP5782521B2 (en) | 2015-09-24 |
| JPWO2013051239A1 (en) | 2015-03-30 |
| EP2765161A4 (en) | 2015-10-28 |
| US20140308501A1 (en) | 2014-10-16 |
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| EP2765161A1 (en) | 2014-08-13 |
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